Recycling method of waste anode beam cleaning wastewater

Abstract

The invention relates to a method for recovering waste anode beam cleaning wastewater. Comprising the following steps: (1) recovering lead and tin of the old anode beam: soaking the old anode beam subjected to pyrogenic process in hydrochloric acid with the concentration of 15-40%, heating to 60-80 DEG C, soaking for 4-8 hours, and recovering a copper beam obtained after soaking treatment; (2) coagulation and replacement: adding a coagulant into the remaining soaking waste liquid, adding chlorine-rich zinc-containing waste and zinc alloy particles in equal proportion so as to replace lead ions and tin ions and coagulate into lead-tin slag, and when the replacement reaction tends to be completed, adding a proper amount of zinc alloy particles again so as to ensure that the replacement reaction of the soaking waste liquid is supersaturated; (3) preparing a zinc chloride finished product: adding zinc powder into the replacement liquid obtained after the lead-tin slag is filtered out twice for purification and impurity removal, and filtering out filter residues obtained after purification each time to obtain a zinc chloride solution; and concentrating and pulverizing the zinc chloride solution to obtain a zinc chloride finished product. The invention aims to fully recover anode beam cleaning wastewater and improve the economic value of the anode beam cleaning wastewater.

Description

Technical Field

[0001] The invention relates to the technical field of metallurgical engineering, and in particular to a method for recovering waste water from washing old anode beams. Background Art

[0002] In the process of wet zinc smelting, cathode and anode plates are generally used. The anode plate is composed of an anode beam and an anode plate surface. The anode beam is made by tinning copper and then casting lead on the copper beam; the anode plate surface is cast from a lead-silver alloy, and then the anode beam and the anode plate surface are welded to form an anode plate. Anode plates will be scrapped and updated after 2-3 years of use. Usually, the old anode plates are separated by a shearing machine, and the old anode plate surface is melted to generate a new anode plate surface. However, the old anode beam is corroded by the electrolytic environment in the electrolyte for many years, and its internal properties have changed greatly. It cannot be directly melted to obtain a new anode beam, and it can usually only be sold directly at a lower price.

[0003] The recycling of old anode beams mainly involves the recovery of lead, tin and other metals on the old anode beams. Usually, the molten lead and tin are recovered by pyrometallurgy after the lead and tin are heated to their melting points. However, when pyrometallurgy is used for recycling, a large amount of lead and tin will remain on the surface of the old copper beams after the lead and tin are melted (see Figure 1 Schematic diagram of the old anode beam after the fire process is shown).

[0004] In the related technical scheme, the lead and tin remaining on the surface of the old copper beam are also soaked and cleaned by pickling, but the chlorine content in the obtained cleaning waste liquid is relatively high (usually 4-21% chlorine). The increased hazardous waste treatment cost when treating the cleaning waste liquid is contrary to the original intention of recycling the old anode beams. Therefore, a method for recycling the cleaning wastewater of the old anode beams is needed to reduce the hazardous waste treatment cost of high-chlorine wastewater while further improving the recycling rate of the old anode beams.

[0005] The above contents are only used to assist in understanding the technical solution of the present invention and do not constitute an admission that the above contents are prior art. Summary of the invention

[0006] The main purpose of the present invention is to provide a method for recycling waste water from washing old anode beams, aiming to solve the problem of how to improve the recycling rate of old anode beams.

[0007] To achieve the above object, the present invention provides a method for recovering waste water from washing old anode beams, the method comprising:

[0008] (1) Lead and tin recovery from old anode beams

[0009] The old anode beam after the pyrometallurgy is soaked in 15-40% hydrochloric acid, heated to 60-80°C and soaked for 4-8 hours, and the copper beam obtained after the soaking treatment is recovered;

[0010] (2) Cohesion replacement

[0011] Adding a coagulant to the remaining soaking waste liquid, as well as an equal proportion of chlorine-rich zinc-containing waste and zinc alloy particles to displace lead ions and tin ions and condense into lead-tin slag, wherein when the replacement reaction is almost complete, adding an appropriate amount of zinc alloy particles again to ensure that the replacement reaction of the soaking waste liquid is supersaturated;

[0012] (3) Preparation of zinc chloride finished product

[0013] Adding zinc powder twice to the replacement solution obtained after filtering the lead-tin residue to purify and remove impurities, and filtering out the filter residue obtained after each purification to obtain a zinc chloride solution;

[0014] The zinc chloride solution is concentrated and powdered to obtain a zinc chloride product.

[0015] Optionally, the ratio between the coagulant and the soaking waste liquid is 3:50, and 1 / 30 of the total amount of the coagulant is dripped into the soaking waste liquid in equal amounts every 1 minute, and the total dripping time is 30 minutes.

[0016] Optionally, the added amount of the chlorine-rich zinc-containing waste and the zinc alloy particles is 300 g / L.

[0017] Optionally, the step of adding zinc powder twice to the replacement liquid obtained after filtering the lead-tin slag to purify and remove impurities specifically includes:

[0018] Adding zinc powder in an amount of 2 g / L to the replacement fluid, controlling the temperature at 80-90 degrees Celsius and reacting for 2 hours or more to remove aluminum ions and copper ions in the replacement fluid;

[0019] After filtering and removing impurities, zinc powder is added to the filtered replacement liquid in an amount of 1 g / L, the temperature is controlled at 70-75 degrees Celsius and the reaction is carried out for 3 hours or more to remove tin ions, lead ions and copper ions in the replacement liquid.

[0020] Optionally, the step of concentrating and powdering the zinc chloride solution to obtain a finished zinc chloride product specifically comprises:

[0021] Evaporating the zinc chloride solution to concentrate the zinc chloride solution to 65%-75%;

[0022] The concentrated zinc chloride solution is subjected to high-frequency vibration pulverization for 20-30 minutes to refine the evaporated crystals;

[0023] The refined zinc chloride crystals are dried and crushed to obtain the zinc chloride finished product.

[0024] Optionally, the heating method in (1) is steam heating.

[0025] Optionally, before (1), the method further includes:

[0026] Add the old anode beam into the power frequency furnace, control the temperature to 400-500℃, and keep it warm for 2-5min;

[0027] The lead-tin alloy ingot obtained after the lead and tin on the old anode beam are melted is recovered, and after recovery, the old anode beam after the pyrometallurgy is obtained by separation.

[0028] This application has at least the following beneficial effects:

[0029] 1. Use 15-40% hydrochloric acid to pickle the old anode beam after the pyrometallurgy to convert the residual lead and tin attached to the old copper beam into lead-tin alloy ingots and SnCl 2 , so that the copper beam remaining after pickling can be recycled;

[0030] 2. Adding equal proportions of chlorine-rich zinc-containing waste and zinc alloy particles to the soaking waste liquid after the copper beam is fished out, so as to replace the lead ions and tin ions and condense into lead-tin slag, and when the replacement reaction is almost completed, adding an appropriate amount of zinc alloy particles again to ensure that the replacement reaction of the soaking waste liquid is supersaturated, so as to replace as many lead ions and tin ions in the soaking waste liquid as possible;

[0031] 3. Adding zinc powder twice to the replacement liquid obtained after filtering the lead-tin slag to purify and remove impurities, the first addition of zinc powder is to remove aluminum ions and copper ions in the replacement liquid, and the second addition is to remove tin ions, lead ions and copper ions in the replacement liquid, thereby improving the purity of the obtained zinc chloride solution;

[0032] 4. Heat the old anode beam after pyrolysis to 60-80℃ in the acid leaching solution and soak it for 4-8h to ensure the reaction rate while avoiding the volatilization of the acid solution;

[0033] 5. Steam heating is adopted for heating. Steam heating generated by smelting waste heat can reduce the cleaning cost. Steam can stir the soaked acid solution, which is beneficial to clean the reactants covering the surface of the old copper beam and accelerate the reaction speed.

[0034] 6. Filter the waste liquid after soaking after the copper beam is recovered, add water and stannous chloride to the obtained filtered liquid after alkali treatment to generate basic tin chloride precipitate and recover it, thereby purifying the waste liquid generated after soaking and generating recyclable basic tin chloride precipitate;

[0035] 7. Add the old anode beam into the power frequency furnace, control the temperature to 400-500℃, and keep it warm for 2-5min to recover the lead and tin on the old copper beam;

[0036] 8. Chlorine-rich zinc-containing waste is a waste produced in large quantities in the production process of the applicant's plant. Therefore, the chlorine-rich zinc-containing waste and the soaking waste liquid generated after the old anode beams after the pickling pyrometallurgy are recycled together to further improve the economic benefits brought by recycling; BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 This is a schematic diagram of the old anode beam after the fire process;

[0038] Figure 2 This is a schematic diagram of the effect obtained after soaking the old copper beam after the pyrolysis process involved in the embodiment of the present application in 30% hydrochloric acid at room temperature for 12 hours;

[0039] Figure 3 This is a schematic diagram of the effect obtained after the old copper beam after the pyrolysis process involved in the embodiment of the present application is soaked in 30% concentration hydrochloric acid at 60 degrees Celsius for 5 hours;

[0040] Figure 4 This is a flow chart of the method for recycling waste water from washing old anode beams involved in Example 3 of the present application;

[0041] Figure 5 This is a flow chart of a method for recycling waste water from washing old anode beams according to Example 9 of the present application;

[0042] Figure 6 This is a flow chart of a method for recycling old anode beams according to Example 10 of the present application;

[0043] The realization of the purpose, functional features and advantages of the present invention will be further explained in conjunction with embodiments and with reference to the accompanying drawings. DETAILED DESCRIPTION

[0044] In order to better understand the above technical solution, exemplary embodiments of the present disclosure will be described in more detail below with reference to the accompanying drawings. Although exemplary embodiments of the present disclosure are shown in the accompanying drawings, it should be understood that the present disclosure can be implemented in various forms and should not be limited by the embodiments described herein. On the contrary, these embodiments are provided to enable a more thorough understanding of the present disclosure and to fully convey the scope of the present disclosure to those skilled in the art.

[0045] Example 1

[0046] In this embodiment, the weight of the old copper beam after the pyrometallurgy process before and after being soaked in hydrochloric acid, nitric acid and sulfuric acid at room temperature is weighed to explore which acid is better for soaking the old anode beam after the pyrometallurgy process, and Table 1 is obtained:

[0047] Table 1. Comparative experiment of old copper beams after pyrometallurgy soaked in three kinds of acids at room temperature for 12 hours

[0048]

[0049] After analyzing the experimental data in the table above and combining it with the actual appearance of the test samples after immersion, we found that the old copper beams after the pyrometallurgy react slowly in sulfuric acid, with a small weight change and more lead and tin residues on the copper beams; the old copper beams after the pyrometallurgy have strong oxidizing properties in nitric acid, and the lead and tin residues on the copper beams are slightly reduced, but nitric acid will react with copper, causing the copper on the copper beams to decrease. The old copper beams after the pyrometallurgy react more violently in hydrochloric acid, and hydrochloric acid does not react with copper, which will not cause the copper on the copper beams to decrease.

[0050] Therefore, hydrochloric acid is preferred as the soaking acid.

[0051] Furthermore, a comparative experiment was conducted on the old copper beams after pyrolysis by immersing them in hydrochloric acid of different concentrations for 12 hours, and the results are shown in Table 2:

[0052] Table 2. Comparative experiment of old copper beams after pyrolysis soaked in different concentrations of hydrochloric acid at room temperature for 12 hours

[0053]

[0054]

[0055] After analyzing the experimental data in the above table, it was found that when the old copper beams after the pyrolysis process were soaked in hydrochloric acid, the intensity of the reaction increased with the increase of concentration. The higher the concentration, the less lead and tin residues on the old copper beams. However, when the concentration of hydrochloric acid was higher than 40%, the change was not obvious.

[0056] Through experiments, it is found that the appropriate concentration is 15-40%, preferably 30%.

[0057] Therefore, it is preferred to soak the old anode beam after the pyrolysis process in hydrochloric acid with a concentration of 15-40%.

[0058] For example, refer to Figure 2 The schematic diagram of the effect obtained after the old copper beam after the fire process is soaked in 30% hydrochloric acid at room temperature for 12 hours. It can be seen that the lead and tin residues attached to the old copper beam after the fire process have been greatly reduced.

[0059] Example 2

[0060] Based on Example 1, the preferred acid type and concentration range have been explored in Example 1, but there are still two problems: one is that the soaking time is long, and the other is that some lead and tin are still attached to the old copper beam after pickling. Therefore, in this comparative example, the old copper beam after the pyrometallurgy is soaked in hydrochloric acid at different reaction temperatures for research, and 30% concentration of hydrochloric acid is selected, and comparative experiments are carried out at 40℃, 50℃, 60℃, 70℃, 80℃, and 90℃, respectively. The data obtained are as shown in Table 3:

[0061] Table 3. Comparative test of old copper beams at different temperatures immersed in 30% hydrochloric acid for 5 hours

[0062]

[0063] The above experiments show that as the temperature increases, the reaction speeds up and the cleaning effect is obvious. However, too high a temperature will reduce the concentration of hydrochloric acid, and the cleaning effect will not be significantly improved, which will increase energy consumption.

[0064] Therefore, it is appropriate to select a soaking temperature between 60 and 80°C, wherein 60°C is preferred to avoid excessive volatilization of hydrochloric acid.

[0065] For example, refer to Figure 3 The schematic diagram of the effect obtained after the old copper beam after the fire process is soaked in 30% concentration hydrochloric acid at 60 degrees Celsius for 5 hours shows that most of the lead and tin residues attached to the old copper beam after the fire process have been removed.

[0066] Example 3

[0067] Based on any of the foregoing embodiments, refer to Figure 4 In this embodiment, a method for recycling waste water from cleaning old anode beams to produce zinc chloride is proposed, comprising the following steps:

[0068] (1) Lead and tin recovery from old anode beams

[0069] Step S10, soaking the old anode beam after the pyrometallurgy in hydrochloric acid with a concentration of 15-40%, heating it to 60-80° C. and soaking it for 4-8 hours, and recovering the copper beam obtained after the soaking treatment;

[0070] In this embodiment, the old anode beam after the pyrolysis is soaked in hydrochloric acid with a concentration of 15-40%, and the soaking temperature is controlled at 60-80° C. After soaking for 4-8 hours, the copper beam obtained after the soaking treatment is recovered.

[0071] The principle is: use 15-40% hydrochloric acid to soak the old copper beams after the pyrometallurgy, convert the residual lead on the old copper beams after the pyrometallurgy into lead slag, and convert the residual tin into SnCl2 and remain in the filtered liquid. The copper beams are washed and reused to produce anode beams.

[0072] For example, in some embodiments, referring to Figure 3 The schematic diagram of the effect obtained after the old copper beam after the fire process is soaked in 30% concentration hydrochloric acid at 60 degrees Celsius for 5 hours shows that most of the lead and tin residues attached to the old copper beam after the fire process have been removed.

[0073] (2) Cohesion replacement

[0074] Step S20, adding a coagulant to the remaining soaking waste liquid, and adding equal proportions of chlorine-rich zinc-containing waste and zinc alloy particles to displace lead ions and tin ions and condense into lead-tin slag, wherein when the replacement reaction is almost completed, adding an appropriate amount of zinc alloy particles again to ensure that the replacement reaction of the soaking waste liquid is supersaturated;

[0075] In this embodiment, the copper beam obtained after the soaking treatment is fished out, the remaining soaking waste liquid is subjected to coagulation replacement, and the chloride ions, lead ions and tin ions in the soaking waste liquid are subjected to coagulation replacement.

[0076] Add chlorine-rich zinc-containing waste and zinc alloy particles in equal proportions (i.e., 1:1) to the soaking waste liquid. It should be noted that the addition process needs to be carried out slowly to avoid violent reactions.

[0077] Optionally, the chlorine-rich zinc-containing waste and the zinc alloy particles may be mixed before being added to the soaking waste liquid, or may be directly poured into the soaking waste liquid at the same time.

[0078] The purpose of adding the coagulant is to quickly coagulate the displaced lead and tin ions into lead slag and tin slag.

[0079] In addition, when the replacement reaction is almost completed, an appropriate amount of zinc alloy particles is added again to ensure that the replacement reaction of the soaking waste liquid is supersaturated, so that the replacement can be fully carried out.

[0080] (3) Preparation of zinc chloride finished product

[0081] Step S30, adding zinc powder twice to the replacement liquid obtained after filtering the lead-tin residue to purify and remove impurities, and filtering out the filter residue obtained after each purification to obtain a zinc chloride solution;

[0082] Step S40, concentrating and powdering the zinc chloride solution to obtain a finished zinc chloride product.

[0083] In this embodiment, after the coagulation replacement is completed, the lead-tin slag is filtered out to obtain a replacement liquid with only liquid components retained, and zinc powder is added to the replacement liquid twice for purification and impurity removal, and the filter residue obtained after each purification is filtered out to obtain a zinc chloride solution.

[0084] The purpose of adding zinc powder for the first time is to remove aluminum ions and copper ions in the replacement liquid, and the purpose of adding zinc powder for the second time is to remove tin ions, lead ions and a small portion of remaining copper ions in the replacement liquid.

[0085] Finally, the zinc chloride solution is concentrated and powdered to obtain the finished zinc chloride product, completing the recovery of the waste water from the cleaning of the old anode beams.

[0086] Example 4

[0087] Based on Example 3, in this example, the ratio between the coagulant and the soaking waste liquid is 3:50, and 1 / 30 of the total amount of the coagulant is dripped into the soaking waste liquid in equal amounts every 1 minute, and the total dripping time is 30 minutes.

[0088] Example 5

[0089] Based on Example 3 or 4, in this example, the addition amount of the chlorine-rich zinc-containing waste and the zinc alloy particles is 300 g / L.

[0090] Example 6

[0091] Based on Examples 3 to 4, in this embodiment, the zinc powder is added twice to the replacement liquid obtained after filtering the lead-tin slag for purification and impurity removal, specifically including:

[0092] Step S31, adding zinc powder in an amount of 2 g / L to the replacement fluid, controlling the temperature at 80-90 degrees Celsius and reacting for 2 hours or more to remove aluminum ions and copper ions in the replacement fluid;

[0093] Step S32, after filtering and removing impurities, add zinc powder in an amount of 1 g / L to the filtered replacement liquid, control the temperature at 70-75 degrees Celsius and react for 3 hours or more to remove tin ions, lead ions and copper ions in the replacement liquid.

[0094] In this embodiment, during the first purification and impurity removal process, zinc powder is added in an amount of 1-3 g / L, the temperature is controlled at 80-90 degrees Celsius and the reaction is carried out for 2 hours or more, thereby removing aluminum ions and copper ions in the replacement liquid.

[0095] It should be noted that the amount of zinc powder added is selected according to the content of impurities Al and Cu in the solution. When the content of aluminum and copper impurities in the solution is high, the amount of zinc powder added can also be adaptively increased.

[0096] It should be noted that the reason for controlling the temperature at 80-90 degrees Celsius and reacting for 2 hours or more is that continuous production emphasizes economic issues. If the time is too short, impurities cannot be completely removed, and if the time is too long, the production efficiency is low and it is not economical. Therefore, it is advisable to control the time at 2 hours.

[0097] Preferably, the temperature can be controlled at 80 degrees Celsius and the reaction time is 2 hours.

[0098] In this embodiment, after the first purification and impurity removal is completed, after filtering and impurity removal, zinc powder is added again in an amount of 1 g / L, the temperature is controlled at 70-75 degrees Celsius and the reaction is carried out for 3 hours or more to remove tin ions, lead ions and copper ions in the replacement liquid.

[0099] Preferably, the temperature is 75 degrees Celsius and the reaction time is 3 hours.

[0100] Example 7

[0101] Based on Examples 3 to 6, in this embodiment, the step of concentrating and powdering the zinc chloride solution to obtain a zinc chloride product specifically includes:

[0102] Step S41, evaporating the zinc chloride solution to concentrate the zinc chloride solution to 65%-75%;

[0103] Step S42, pulverizing the concentrated zinc chloride solution by high-frequency vibration for 20-30 minutes to refine the evaporated crystals;

[0104] Step S43, drying and crushing the refined zinc chloride crystals to obtain the finished zinc chloride product.

[0105] In this embodiment, after the secondary impurity removal and purification, the zinc chloride solution is evaporated and concentrated to 65%-75%. At this concentration, both crystallization efficiency and production energy consumption can be taken into account.

[0106] Preferably, the concentration after evaporation is 70%.

[0107] Then the concentrated zinc chloride solution is subjected to high-frequency vibration pulverization for 20-30 minutes. Optionally, the concentrated zinc chloride solution can be subjected to high-frequency vibration by ultrasonic waves to break the zinc chloride solution into evaporation crystals, thereby making it easier to dry and crush it.

[0108] Finally, the refined zinc chloride crystals are dried and crushed to obtain zinc chloride products, completing the recovery of chloride ions in the wastewater from the old anode beam cleaning.

[0109] Example 8

[0110] Based on any one of Examples 3 to 7, in this embodiment, (1) the heating method in the lead-tin recovery of the old anode beam is steam heating.

[0111] Using steam generated by smelting waste heat to heat the old anode beams soaked in hydrochloric acid after the pyrolysis process can reduce cleaning costs. In addition, steam can stir the soaking acid, which is beneficial for cleaning the reactants covering the surface of the old copper beams and accelerating the reaction rate.

[0112] Example 9

[0113] Based on any one of Examples 3 to 8, refer to Figure 5 In this embodiment, before step S10, the following steps are also included:

[0114] Step S50, adding the old anode beam into the industrial frequency furnace, controlling the temperature to 400-500°C, and keeping the temperature for 2-5 minutes;

[0115] Step S60, recovering the lead-tin alloy ingot obtained by melting the lead and tin on the old anode beam, and separating to obtain the old anode beam after the pyrometallurgy.

[0116] In this embodiment, the old anode beam is added to the industrial frequency furnace, the temperature is controlled to be 400-500°C to reach the melting point of lead and tin, and the temperature is kept for 2-5 minutes to melt the lead and tin hanging on the anode beam. The melted liquid produces a lead-tin alloy ingot. After the lead and tin are melted, some lead and tin remain on the remaining old copper beam, and no copper is exposed. The old anode beam after the pyrometallurgy is obtained by separation.

[0117] Example 10

[0118] Reference Figure 6 A schematic flow chart of a method for recycling wastewater from washing old anode beams in another specific embodiment is shown. In this embodiment, first, the old anode beams are added to an industrial frequency furnace, the temperature is controlled to be 400-500°C, and the temperature is kept for 2-5 minutes; the lead and tin hanging on the anode beams are melted, and the melted liquid produces lead-tin alloy ingots; after the lead and tin are melted, some lead and tin remain on the remaining old copper beams, and no copper is exposed;

[0119] Furthermore, the old copper beams are soaked in 15-40% hydrochloric acid, steam-heated at 60-80°C and soaked for 4-8 hours, the copper beams are fished out, rinsed and reused to produce anode beams, and the rinse water is returned for soaking; the waste liquid from the soaking is filtered and used to produce zinc oxide.

[0120] Furthermore, zinc alloy particles and chlorine-rich zinc-containing waste (containing 4-21% chlorine) are slowly added to the old copper beam soaking waste liquid in a ratio of 1:1 to fully react for 4-6 hours, and zinc alloy particles are added later for supersaturated coagulation and replacement; a coagulant is added during the process to make the lead and tin slags quickly coagulate, which is convenient for filtering and separating the slag liquid, and the lead and tin slags are exported.

[0121] Furthermore, after the replacement liquid is filtered, metallic zinc powder is added and purified twice to remove impurities, and the purification temperature is controlled at 60-90° C. The zinc chloride solution purified twice is purer, and the zinc chloride product has a higher purity.

[0122] Furthermore, after the concentrated zinc chloride solution is pulverized by high-frequency vibration, the evaporated crystals will be finer, easier to be crushed into powder, and have a finer particle size.

[0123] Finally, drying and crushing are carried out to obtain the finished product after drying and crushing the zinc chloride crystals.

[0124] The zinc chloride prepared by the method has high purity, fine particle size and good economic benefits.

[0125] It should be noted that, although the preferred embodiments of the present invention have been described, those skilled in the art may make additional changes and modifications to these embodiments once they have learned the basic creative concept. Therefore, the appended claims are intended to be interpreted as including the preferred embodiments and all changes and modifications that fall within the scope of the present invention.

[0126] Obviously, those skilled in the art can make various changes and modifications to the present invention without departing from the spirit and scope of the present invention. Thus, if these modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include these modifications and variations.

Claims

1. A method for recycling waste water from washing old anode beams, characterized in that: The method comprises the following steps: (1) Lead and tin recovery from old anode beams The old anode beam after the pyrometallurgy is soaked in 15-40% hydrochloric acid, heated to 60-80°C and soaked for 4-8 hours, and the copper beam obtained after the soaking treatment is recovered; (2) Cohesion replacement Adding a coagulant to the remaining soaking waste liquid, as well as an equal proportion of chlorine-rich zinc-containing waste and zinc alloy particles to displace lead ions and tin ions and condense into lead-tin slag, wherein when the replacement reaction is almost complete, adding an appropriate amount of zinc alloy particles again to ensure that the replacement reaction of the soaking waste liquid is supersaturated; (3) Preparation of zinc chloride finished product Adding zinc powder twice to the replacement solution obtained after filtering the lead-tin residue to purify and remove impurities, and filtering out the filter residue obtained after each purification to obtain a zinc chloride solution; The zinc chloride solution is concentrated and powdered to obtain a zinc chloride product.

2. The method according to claim 1, characterized in that The ratio between the coagulant and the soaking waste liquid is 3:50, and 1 / 30 of the total amount of the coagulant is dripped into the soaking waste liquid in equal amounts every 1 minute, and the total dripping time is 30 minutes.

3. The method according to claim 1, characterized in that The addition amount of the chlorine-rich zinc-containing waste and the zinc alloy particles is 300 g / L.

4. The method according to claim 1, characterized in that The step of adding zinc powder twice to the replacement liquid obtained after filtering the lead-tin slag to purify and remove impurities specifically includes: Adding zinc powder in an amount of 2 g / L to the replacement fluid, controlling the temperature at 80-90 degrees Celsius and reacting for 2 hours or more to remove aluminum ions and copper ions in the replacement fluid; After filtering and removing impurities, zinc powder is added to the filtered replacement liquid in an amount of 1 g / L, the temperature is controlled at 70-75 degrees Celsius and the reaction is carried out for 3 hours or more to remove tin ions, lead ions and copper ions in the replacement liquid.

5. The method according to claim 1, characterized in that The step of concentrating and powdering the zinc chloride solution to obtain a zinc chloride product specifically comprises: Evaporating the zinc chloride solution to concentrate the zinc chloride solution to 65%-75%; The concentrated zinc chloride solution is subjected to high-frequency vibration pulverization for 20-30 minutes to refine the evaporated crystals; The refined zinc chloride crystals are dried and crushed to obtain the zinc chloride finished product.

6. The method according to claim 1, characterized in that The heating method in (1) is steam heating.

7. The method according to claim 1, characterized in that Before (1), it also includes: Add the old anode beam into the power frequency furnace, control the temperature to 400-500℃, and keep it warm for 2-5min; The lead-tin alloy ingot obtained after the lead and tin on the old anode beam are melted is recovered, and after recovery, the old anode beam after the pyrometallurgy is obtained by separation.

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